Poly­[[bis­[aqua(1,10-phenanthroline)­lanthanum(III)]-μ-aqua-di-μ-5-sulfonatoisophthalato] monohydrate] and poly­[[[tri­aqua­lanthanum(III)]-μ-5-sulfonatoisophthalato] monohydrate]

In the two related polymeric title compounds, {[La₂(sip)₂(phen)₂(H₂O)₃]·H₂O}_n [sip is the 5-sulfonatoisophthalate trianion (C₈H₃O₇S³⁻) and phen is 1,10-phenanthroline (C₁₂H₈N₂)], (I), and {[La(sip)(H₂O)₃]·H₂O}_n, (II), the lanthanum(III) ions are nine-coordinate, with similar distorted monocapped square-antiprism coordination geometry. The two crystal structures are very different. In (I), the sip anion acts as a pentadentate ligand, one of the coordinated water mol­ecules lies on a twofold axis and further inversion, n-glide and translation operations generate a two-dimensional framework. In (II), the sip anion functions as a hexadentate ligand and a three-dimensional network with trinuclear 24-membered rings is developed via inversion, n-glide, twofold-screw and translation operations. Both structures also have extensive O—H...O hydrogen-bonded networks and π–π interactions.

S1. Comment

A number of coordination polymers assembled from lanthanide ions and aromatic polycarboxylate ligands have been extensively studied in recent years, due to their intriguing structural diversity and potential application as functional materials (Hu Zhu et al., 2004; Wan et al., 2003; Zhang et al., 2003). However, lanthanide coordination polymers utilizing organic species with two or more different functional groups, both coordinated to the metal ions, are very rare (Hu Yuan et al., 2004). It is of interest to us that the polytypic sip anion, which is nearly rigid and which has both carboxylate and sulfonate as potential coordinating groups, can form not only short bridges via one carboxylate or sulfonate end, but also long bridges via the central aromatic ring between metal ions. In principle, the novelty of coordination polymers depends on the deliberate selection of central metal ions and multifunctional ligands. The lanthanide ions are well known for their large radii and variable coordination number in the range of 3 to 12, which make these ions excellent spacers in assembling fascinating metal-organic frameworks (Wan et al., 2002). Thus, we have selected the La-sip-phen system and the La-sip system to extend this research and we present here the crystal structures of the two title compounds, {[La₂(sip)₂(phen)₂(H₂O)₃]·H₂O}_n, (I) and {[La(sip)(H₂O)₃]·H₂O}_n, (II), (sip is the 5-sulfonatoisophthalate trianion and phen is 1,10-phenanthroline). \sch

In (I), each La^III ion coordinates to four O atoms from three carboxylate groups of three sip anions, with a typical La—O(carboxylate) distance range [2.442 (4)–2.617 (4) Å; Kim & Jung, 2002), one bridging water molecule (O8) with a longer La—O distance [2.9231 (9) Å], due to its weak coordination role between two La^III ions (Liu et al., 2001), one water molecule (O9) with a normal La—O distance [2.538 (4) Å], one sulfonate O1 atom from another sip anion with an La—O distance of 2.474 (4) Å, and atoms N1 and N10 of the phen ligand in a chelating fashion, with typical La—N distances of 2.730 (5) and 2.712 (5) Å (Shi et al., 2001), resulting in a distorted monocapped square antiprism (Fig. 1). The square plane of atoms N1, N2, O7ⁱⁱⁱ and O8 [symmetry code: (iii) 1 + x, y, z], with a mean deviation of 0.42 Å, is seriously distorted, but the mean deviation of the other square plane composed of atoms O1, O4ⁱⁱ, O5ⁱⁱ and O9 is only 0.05 Å [symmetry code: (ii) 1/2 + x, −y, 1/2 + z]. To complete the coordination environment of the La centre, atom O6ⁱ is located as the cap [symmetry code: (i) −x, −y, −z].

Each sip anion acts as a pentadentate ligand to connect four La^III ions through its one bridging carboxylate group, one chelating carboxylate group and one monodentate sulfonate group. This coordination mode is slightly different from that in the lanthanide coordination polymer [Eu(sip)(H₂O)₄]_n (Wang et al., 2002), in which the two carboxylate groups of each sip anion show bidentate chelation. As shown in Fig. 2, each pair of La^III ions is bridged by a pair of carboxylate groups, forming an eight-membered ring with an La1···La1^v separation of 5.1426 (6) Å [symmetry code: (v) 1 − x, −y, −z], and each pair of such rings is interconnected by two carboxylate-carboxylate bridges of two sip anions via benzene rings to form an intersecting double chain along the [101] direction. Within this double chain, there are also 16-membered rings, each of which is formed by two La^III ions and two carboxylate-carboxylate bridges of two sip anions via benzene rings, with an La1···La1^iv separation of 7.8646 (6) Å [symmetry code: (iv) 1/2 − x, y, 1/2 − z]. This double chain is similar to that found in [Zn(sip)(H-4,4'-bipyridine)(H₂O)]·2H₂O (Sun et al., 2004).

Moreover, as shown in Fig. 3, each pair of La^III ions is linked by a carboxylate-sulfonate bridge of a sip anion via a benzene ring, with an La1···La1^vi separation of 8.5572 (6) Å [symmetry code: (vi) x − 1/2, −y, z − 1/2], extending in a wave-like chain, and two adjacent chains are connected by bridging water molecules to produce a ribbon-like double chain containing 20-membered rings, each of which comprises two carboxylate-sulfonate bridges of two sip anions, two bridging water molecules and four La^III ions, along the [101] direction. The two different kinds of double chains are staggered relative to each other, to generate a two-dimensional network with octanuclear units, each of which comprises four sip anions, eight La^III ions and two bridging water molecules (Fig. 4).

In the crystal of (I), the noncomplexed water molecule (O10) lies on a twofold axis and all water O—H groups participate in O—H···O hydrogen bonds with sip anions (details in Table 2). There are also π–π interactions between inversion-related sip aromatic rings [at (x, y, z) and (-x, −y, −z)], with the ring centroids separated by 3.523 Å (3.214 Å between planes), and also between inversion-related rings of the phen moieties [at (x, y, z) and (1 − x, 1 − y, −z)], with the ring centroids separated by 3.478 Å and with a 3.214 Å separation between the planes.

In (II), the coordination geometry of the unique La^III ion is a distorted monocapped square antiprism, similar to that of (I) (Fig. 5). The square plane of atoms O1, O4^viii, O5^viii and O8, with a mean deviation of 0.20 Å, is seriously distorted, but the mean deviation of the other square plane composed of atoms O2^ix, O6^x, O7^xi and O10 is only 0.10 Å [symmetry codes: (viii) 1/2 − x, y − 1/2, 3/2 − z; (ix) x − 1/2, 1/2 − y, 1/2 + z; (x) −x, 1 − y, 1 − z; (xi) x, y, 1 + z]. Atom O9 as the cap completes the coordination at La.

Each sip anion of (II) acts as a hexadentate ligand to connect five La^III ions through one bridging carboxylate group, one chelating carboxylate group and one bidentate sulfonate group. This coordination mode is quite different from the pentadentate fashion of (I) and that in [Cu₄(OH)₂(sip)₂(bipy)₂]·2H₂O (bipy is 4,4'-bipyridine; Sun et al., 2003), in which the two carboxylate groups of each sip anion are bidentate chelating and the sulfonate group uses one O atom to make significant contact with two Cu atoms.

As shown in Fig. 6, three La^III ions in (II) are bridged by three sip anions, forming a trinuclear 24-membered ring with three different La1^viii···La1^xi, La1^viii···La1 and La1^xi···La1 separations of 10.5645 (3), 9.8022 (3) and 10.5753 (3) Å, respectively. Each trinuclear ring links six adjacent rings, extending to form a two-dimensional layer in the crystallographic bc plane. This is comparable with what was found in a Eu-sip-H₂O analogue (Wang et al., 2002).

Each pair of La^III ions in (II) is connected by three different kinds of bridges, namely carboxylate short-bridge, carboxylate-carboxylate and carboxylate-sulfonate long-bridge, generating three different kinds of binuclear rings, with La1^xiii···La1^xiv, La1^xiii···La1^xv and La1^xiii···La1 separations of 5.0235 (3), 7.0487 (3) and 10.5235 (3) Å, respectively [symmetry codes: (xiii) 1 − x, 1 − y, 1 − z; (xiv) x, y − 1, z; (xv) 3/2 − x, y − 1/2, 3/2 − z]. Each binuclear eight-membered ring links six binuclear 16-membered rings to produce another two-dimensional layer in the ab plane (Fig. 7), which is different from the double chain found in (I) and [Zn(sip)(H-bipy)(H₂O)]·2H₂O (Sun et al., 2004). Thus each sip anion in (II) acts as a hexadentate bridge, interconnecting the two different kinds of layers to yield a three-dimensional framework.

As in (I), the water O—H groups in (II) participate in O—H···O hydrogen bonds (with sip anions or uncoordinated water molecules; details in Table 4). There are also π–π interactions between inversion-related sip anions [at (x, y, z) and (1 − x, 2 − y, 2 − z)], with the ring centroids separated by 3.697 Å and a 3.566 Å separation between the planes.

S2. Experimental

The two title compounds were synthesized using the hydrothermal method. For (I), the mixture consisted of sodium 5-sulfoisophthalate (1 mmol, 0.27 g), LaCl₃·6H₂O (1 mmol, 0.35 g), 1,10-phenanthroline (3 mmol, 0.54 g) and water (20 ml). For (II), the mixture consisted of sodium 5-sulfoisophthalate (1 mmol, 0.27 g), LaCl₃·6H₂O (1 mmol, 0.35 g), 2-aminopyrimidine (3 mmol, 0.29 g) and water (20 ml). The mixtures were placed in 30 ml Teflon-lined stainless steel reactors. The solution for (I) was heated to 412 K for 3 d, and the solution for (II) was heated to 408 K for 4 d. After slow cooling of the reaction systems to room temperature, colourless prism crystals of (I) and (II) were collected and washed with distilled water.

S3. Refinement

The water H atoms were refined subject to the restraint O—H = 0.82 (2) Å. The remaining H atoms were positioned geometrically and allowed to ride on their parent atoms at distances of 0.93 Å, with U_iso(H) = 1.2U_eq(parent atom). The 1.628 e Å⁻³ peak in the final difference Fourier map for (I) was adjacent to La1.

Computing details

For both compounds, data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 2002); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The coordination environment of the La^III ion in (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) −x, −y, −z; (ii) 1/2 + x, −y, 1/2 + z; (iii) 1 + x, y, z.]
	Fig. 2. The intersecting double chain of (I) along the [101] direction. H atoms, non-bridging water molecules and 1,10-phenanthroline molecules have been omitted for clarity. [Symmetry codes: (i) −x, −y, −z; (ii) 1/2 + x, −y, 1/2 + z; (iii) 1 + x, y, z; (iv) 1/2 − x, y, 1/2 − z; (v) 1 − x, −y, −z.]
	Fig. 3. The ribbon-like double chain of (I) along the [101] direction. H atoms, non-bridging water molecules and 1,10-phenanthroline molecules have been omitted for clarity. [Symmetry codes: (v) 1 − x, −y, −z; (vi) x − 1/2, −y, z − 1/2; (vii) 3/2 − x, y, 1/2 − z.]
	Fig. 4. Perspective view of the two-dimensional network in (I) along the b axis. H atoms, non-bridging water molecules and 1,10-phenanthroline molecules have been omitted for clarity.
	Fig. 5. The coordination environment of the La^III ion in (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (viii) 1/2 − x, y − 1/2, 3/2 − z; (ix) x − 1/2, 1/2 − y, 1/2 + z; (x) −x, 1 − y, 1 − z; (xi) x, y, 1 + z.]
	Fig. 6. The two-dimensional layer of (II) in the crystallographic bc plane. H atoms and water molecules have been omitted for clarity. [Symmetry codes: (viii) 1/2 − x, y − 1/2, 3/2 − z; (xi) x, y, 1 + z; (xii) 1/2 − x, y − 1/2, 5/2 − z.]
	Fig. 7. The two-dimensional layer of (II) in the crystallographic ab plane. H atoms and water molecules have been omitted for clarity. [Symmetry codes: (xiii) 1 − x, 1 − y, 1 − z; (xiv) x, y − 1, z; (xv) 3/2 − x, y − 1/2, 3/2 − z.]

(I) Poly[[bis[aqua(1,10-phenanthroline)lanthanum(III)]-µ-aqua-di-µ-5- sulfonatoisophthalato] monohydrate]

Crystal data

[La2(C8H3O7S)2(C12H8N2)2(H2O)3]·H2O	F(000) = 1176
Mr = 1196.62	Dx = 1.956 Mg m^−3
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2yac	Cell parameters from 6312 reflections
a = 10.1655 (5) Å	θ = 2.5–25.2°
b = 15.1560 (7) Å	µ = 2.26 mm^−1
c = 13.8914 (6) Å	T = 298 K
β = 108.302 (2)°	Prism, colourless
V = 2031.96 (16) Å^3	0.27 × 0.18 × 0.15 mm
Z = 2

Data collection

Bruker APEX CCD area-detector diffractometer	3661 independent reflections
Radiation source: fine-focus sealed tube	3586 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ϕ and ω scans	θmax = 25.2°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −12→12
Tmin = 0.531, Tmax = 0.718	k = −18→14
10692 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.40	w = 1/[σ^2(Fo^2) + (0.0465P)^2 + 5.3444P] where P = (Fo^2 + 2Fc^2)/3
3661 reflections	(Δ/σ)max < 0.001
314 parameters	Δρmax = 1.63 e Å^−3
7 restraints	Δρmin = −0.79 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
La1	0.49529 (3)	0.15233 (2)	0.08034 (2)	0.01710 (13)
S1	0.12533 (14)	0.25196 (9)	−0.04135 (11)	0.0226 (3)
O1	0.2693 (4)	0.2233 (3)	−0.0040 (4)	0.0377 (11)
O2	0.0811 (5)	0.2984 (3)	0.0330 (4)	0.0472 (14)
O3	0.0980 (5)	0.2997 (3)	−0.1363 (4)	0.0402 (12)
O4	0.0785 (4)	−0.0228 (3)	−0.2902 (3)	0.0259 (9)
O5	−0.0653 (4)	−0.1179 (3)	−0.2569 (3)	0.0250 (9)
O6	−0.3421 (4)	−0.0246 (3)	−0.0329 (3)	0.0307 (10)
O7	−0.2881 (4)	0.0993 (3)	0.0543 (3)	0.0238 (9)
O8	0.7500	0.1750 (5)	0.2500	0.0359 (15)
H8A	0.789 (12)	0.137 (7)	0.227 (8)	0.043*	0.50
H8B	0.783 (14)	0.184 (8)	0.311 (3)	0.043*	0.50
O9	0.4450 (5)	0.1345 (3)	−0.1095 (3)	0.0318 (10)
H9A	0.433 (7)	0.0859 (19)	−0.136 (4)	0.038*
H9B	0.394 (6)	0.174 (3)	−0.141 (4)	0.038*
O10	0.2500	0.2332 (5)	−0.2500	0.0399 (16)
H10A	0.213 (8)	0.266 (4)	−0.219 (6)	0.048*
C1	−0.0319 (5)	0.0197 (4)	−0.1684 (4)	0.0176 (11)
C2	−0.1353 (5)	0.0028 (4)	−0.1244 (4)	0.0195 (11)
H2	−0.1892	−0.0477	−0.1423	0.023*
C3	−0.1579 (5)	0.0609 (4)	−0.0544 (4)	0.0191 (11)
C4	−0.0767 (6)	0.1365 (4)	−0.0270 (4)	0.0197 (11)
H4	−0.0904	0.1751	0.0210	0.024*
C5	0.0251 (6)	0.1538 (4)	−0.0721 (4)	0.0203 (12)
C6	0.0475 (6)	0.0960 (4)	−0.1431 (4)	0.0193 (11)
H6	0.1151	0.1082	−0.1734	0.023*
C7	−0.0050 (6)	−0.0449 (4)	−0.2424 (4)	0.0217 (12)
C8	−0.2694 (5)	0.0437 (4)	−0.0072 (4)	0.0191 (11)
N1	0.6120 (5)	0.2927 (3)	0.0144 (4)	0.0322 (12)
C2A	0.6701 (7)	0.2835 (5)	−0.0575 (6)	0.0429 (18)
H2A	0.6638	0.2291	−0.0895	0.051*
C3A	0.7411 (9)	0.3519 (6)	−0.0882 (8)	0.057 (2)
H3A	0.7812	0.3429	−0.1391	0.068*
C4A	0.7497 (8)	0.4309 (6)	−0.0422 (7)	0.057 (2)
H4A	0.7985	0.4765	−0.0602	0.069*
C5A	0.6876 (7)	0.4449 (5)	0.0308 (6)	0.0450 (19)
C6A	0.6848 (9)	0.5295 (5)	0.0762 (7)	0.057 (2)
H6A	0.7260	0.5777	0.0556	0.069*
C7A	0.6237 (9)	0.5399 (5)	0.1478 (7)	0.055 (2)
H7A	0.6238	0.5955	0.1763	0.066*
C8A	0.6226 (6)	0.3719 (4)	0.0617 (5)	0.0303 (14)
C9A	0.5600 (6)	0.3839 (4)	0.1405 (5)	0.0289 (14)
N10	0.5014 (6)	0.3117 (3)	0.1703 (4)	0.0308 (12)
C11A	0.4443 (8)	0.3239 (5)	0.2431 (6)	0.0395 (17)
H11A	0.4049	0.2755	0.2647	0.047*
C12A	0.4400 (10)	0.4052 (5)	0.2890 (6)	0.054 (2)
H12A	0.3986	0.4107	0.3397	0.064*
C13A	0.4971 (9)	0.4753 (5)	0.2585 (6)	0.050 (2)
H13A	0.4958	0.5298	0.2891	0.060*
C14A	0.5583 (8)	0.4683 (4)	0.1820 (5)	0.0392 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
La1	0.0179 (2)	0.0159 (2)	0.0213 (2)	−0.00194 (12)	0.01168 (14)	0.00095 (11)
S1	0.0205 (7)	0.0170 (7)	0.0331 (8)	−0.0026 (5)	0.0125 (6)	−0.0041 (6)
O1	0.022 (2)	0.032 (3)	0.054 (3)	0.0001 (19)	0.005 (2)	−0.002 (2)
O2	0.048 (3)	0.037 (3)	0.070 (4)	−0.014 (2)	0.038 (3)	−0.027 (3)
O3	0.045 (3)	0.026 (2)	0.050 (3)	−0.006 (2)	0.016 (2)	0.012 (2)
O4	0.030 (2)	0.027 (2)	0.029 (2)	−0.0064 (17)	0.0218 (19)	−0.0045 (17)
O5	0.039 (2)	0.016 (2)	0.029 (2)	−0.0055 (18)	0.0229 (19)	−0.0044 (16)
O6	0.031 (2)	0.033 (2)	0.034 (2)	−0.0124 (19)	0.020 (2)	−0.0040 (19)
O7	0.021 (2)	0.025 (2)	0.032 (2)	−0.0006 (16)	0.0177 (18)	−0.0039 (17)
O8	0.042 (4)	0.035 (4)	0.027 (3)	0.000	0.007 (3)	0.000
O9	0.040 (3)	0.027 (2)	0.030 (2)	0.006 (2)	0.013 (2)	−0.0024 (19)
O10	0.056 (5)	0.035 (4)	0.033 (4)	0.000	0.019 (3)	0.000
C1	0.020 (3)	0.018 (3)	0.019 (3)	0.003 (2)	0.011 (2)	0.001 (2)
C2	0.016 (3)	0.020 (3)	0.023 (3)	−0.003 (2)	0.007 (2)	0.000 (2)
C3	0.018 (3)	0.017 (3)	0.025 (3)	0.000 (2)	0.011 (2)	0.003 (2)
C4	0.020 (3)	0.018 (3)	0.025 (3)	0.002 (2)	0.013 (2)	0.000 (2)
C5	0.018 (3)	0.021 (3)	0.023 (3)	−0.002 (2)	0.008 (2)	0.000 (2)
C6	0.019 (3)	0.022 (3)	0.021 (3)	−0.001 (2)	0.011 (2)	0.000 (2)
C7	0.022 (3)	0.022 (3)	0.021 (3)	0.002 (2)	0.008 (2)	0.002 (2)
C8	0.016 (3)	0.018 (3)	0.025 (3)	0.002 (2)	0.008 (2)	0.002 (2)
N1	0.025 (3)	0.026 (3)	0.050 (3)	0.001 (2)	0.018 (3)	0.014 (2)
C2A	0.039 (4)	0.040 (4)	0.063 (5)	0.010 (3)	0.035 (4)	0.022 (4)
C3A	0.048 (5)	0.061 (6)	0.073 (6)	0.001 (4)	0.036 (5)	0.030 (5)
C4A	0.034 (4)	0.059 (6)	0.079 (6)	−0.011 (4)	0.016 (4)	0.037 (5)
C5A	0.033 (4)	0.035 (4)	0.057 (5)	−0.011 (3)	−0.001 (3)	0.017 (3)
C6A	0.052 (5)	0.034 (4)	0.069 (6)	−0.021 (4)	−0.005 (4)	0.020 (4)
C7A	0.056 (5)	0.021 (4)	0.061 (5)	−0.014 (3)	−0.018 (4)	0.008 (3)
C8A	0.021 (3)	0.022 (3)	0.039 (4)	−0.004 (2)	−0.003 (3)	0.011 (3)
C9A	0.027 (3)	0.018 (3)	0.034 (3)	−0.004 (2)	−0.002 (3)	0.004 (2)
N10	0.034 (3)	0.022 (3)	0.035 (3)	0.000 (2)	0.009 (2)	0.000 (2)
C11A	0.058 (5)	0.025 (3)	0.040 (4)	0.005 (3)	0.022 (4)	0.004 (3)
C12A	0.083 (6)	0.033 (4)	0.049 (5)	0.014 (4)	0.027 (5)	0.000 (3)
C13A	0.070 (5)	0.027 (4)	0.043 (4)	0.002 (4)	0.002 (4)	−0.003 (3)
C14A	0.048 (4)	0.021 (3)	0.034 (4)	−0.007 (3)	−0.008 (3)	0.001 (3)

Geometric parameters (Å, º)

La1—O1	2.474 (4)	C3—C4	1.393 (8)
La1—O4^i	2.617 (4)	C3—C8	1.500 (7)
La1—O5^i	2.577 (4)	C4—C5	1.392 (8)
La1—O6^ii	2.442 (4)	C4—H4	0.93
La1—O7^iii	2.475 (4)	C5—C6	1.391 (8)
La1—O8	2.9231 (9)	C6—H6	0.93
La1—O9	2.538 (4)	N1—C2A	1.318 (9)
La1—N1	2.730 (5)	N1—C8A	1.357 (9)
La1—N10	2.712 (5)	C2A—C3A	1.404 (10)
S1—O1	1.457 (4)	C2A—H2A	0.93
S1—O2	1.434 (5)	C3A—C4A	1.347 (13)
S1—O3	1.453 (5)	C3A—H3A	0.93
S1—C5	1.778 (6)	C4A—C5A	1.369 (12)
O4—C7	1.276 (7)	C4A—H4A	0.93
O4—La1^iv	2.617 (4)	C5A—C8A	1.422 (9)
O5—C7	1.249 (7)	C5A—C6A	1.432 (12)
O5—La1^iv	2.577 (4)	C6A—C7A	1.338 (13)
O6—C8	1.257 (7)	C6A—H6A	0.93
O6—La1^ii	2.442 (4)	C7A—C14A	1.430 (11)
O7—C8	1.256 (7)	C7A—H7A	0.93
O8—H8A	0.82 (11)	C8A—C9A	1.440 (10)
O8—H8B	0.82 (5)	C9A—N10	1.371 (8)
O9—H9A	0.82 (3)	C9A—C14A	1.405 (9)
O9—H9B	0.82 (5)	N10—C11A	1.327 (9)
O10—H10A	0.82 (8)	C11A—C12A	1.395 (10)
C1—C6	1.390 (8)	C11A—H11A	0.93
C1—C2	1.395 (7)	C12A—C13A	1.341 (11)
C1—C7	1.506 (8)	C12A—H12A	0.93
C2—C3	1.383 (8)	C13A—C14A	1.395 (11)
C2—H2	0.93	C13A—H13A	0.93
O6^ii—La1—O1	78.35 (15)	C3—C4—H4	120.2
O6^ii—La1—O7^iii	103.00 (13)	C6—C5—C4	120.7 (5)
O1—La1—O7^iii	143.96 (15)	C6—C5—S1	119.2 (4)
O6^ii—La1—O9	74.47 (15)	C4—C5—S1	120.0 (4)
O1—La1—O9	72.54 (16)	C1—C6—C5	119.4 (5)
O7^iii—La1—O9	73.25 (14)	C1—C6—H6	120.3
O6^ii—La1—O5^i	76.57 (14)	C5—C6—H6	120.3
O1—La1—O5^i	93.52 (15)	O5—C7—O4	121.4 (5)
O7^iii—La1—O5^i	122.10 (13)	O5—C7—C1	120.1 (5)
O9—La1—O5^i	149.82 (15)	O4—C7—C1	118.5 (5)
O6^ii—La1—O4^i	68.40 (14)	O5—C7—La1^iv	60.4 (3)
O1—La1—O4^i	134.70 (14)	O4—C7—La1^iv	62.3 (3)
O7^iii—La1—O4^i	75.34 (12)	C1—C7—La1^iv	167.4 (4)
O9—La1—O4^i	123.41 (13)	O7—C8—O6	123.1 (5)
O5^i—La1—O4^i	50.17 (12)	O7—C8—C3	118.5 (5)
O6^ii—La1—N10	138.65 (15)	O6—C8—C3	118.4 (5)
O1—La1—N10	73.39 (16)	C2A—N1—C8A	118.3 (6)
O7^iii—La1—N10	117.64 (15)	C2A—N1—La1	121.2 (5)
O9—La1—N10	122.80 (15)	C8A—N1—La1	120.3 (4)
O5^i—La1—N10	75.72 (14)	N1—C2A—C3A	123.2 (8)
O4^i—La1—N10	113.31 (15)	N1—C2A—H2A	118.4
O6^ii—La1—N1	146.59 (16)	C3A—C2A—H2A	118.4
O1—La1—N1	86.50 (15)	C4A—C3A—C2A	118.4 (8)
O7^iii—La1—N1	72.74 (14)	C4A—C3A—H3A	120.8
O9—La1—N1	72.62 (17)	C2A—C3A—H3A	120.8
O5^i—La1—N1	134.52 (16)	C3A—C4A—C5A	120.9 (7)
O4^i—La1—N1	137.26 (14)	C3A—C4A—H4A	119.6
N10—La1—N1	60.74 (17)	C5A—C4A—H4A	119.6
O6^ii—La1—O8	129.74 (17)	C4A—C5A—C8A	118.0 (7)
O1—La1—O8	141.85 (16)	C4A—C5A—C6A	122.8 (7)
O7^iii—La1—O8	63.42 (11)	C8A—C5A—C6A	119.3 (8)
O9—La1—O8	133.53 (11)	C7A—C6A—C5A	120.7 (7)
O5^i—La1—O8	73.24 (10)	C7A—C6A—H6A	119.6
O4^i—La1—O8	61.37 (16)	C5A—C6A—H6A	119.6
N10—La1—O8	68.73 (17)	C6A—C7A—C14A	122.0 (8)
N1—La1—O8	79.08 (16)	C6A—C7A—H7A	119.0
O2—S1—O3	113.3 (3)	C14A—C7A—H7A	119.0
O2—S1—O1	113.4 (3)	N1—C8A—C5A	121.1 (7)
O3—S1—O1	110.9 (3)	N1—C8A—C9A	119.5 (5)
O2—S1—C5	107.3 (3)	C5A—C8A—C9A	119.3 (6)
O3—S1—C5	105.5 (3)	N10—C9A—C14A	122.7 (6)
O1—S1—C5	105.8 (3)	N10—C9A—C8A	117.8 (6)
S1—O1—La1	168.0 (3)	C14A—C9A—C8A	119.5 (6)
C7—O4—La1^iv	92.1 (3)	C11A—N10—C9A	117.1 (6)
C7—O5—La1^iv	94.6 (3)	C11A—N10—La1	121.5 (4)
C8—O6—La1^ii	176.3 (4)	C9A—N10—La1	121.4 (4)
H8A—O8—H8B	115 (3)	N10—C11A—C12A	123.7 (7)
H9A—O9—H9B	116 (3)	N10—C11A—H11A	118.1
C6—C1—C2	120.0 (5)	C12A—C11A—H11A	118.1
C6—C1—C7	119.9 (5)	C13A—C12A—C11A	118.5 (8)
C2—C1—C7	120.2 (5)	C13A—C12A—H12A	120.8
C3—C2—C1	120.4 (5)	C11A—C12A—H12A	120.8
C3—C2—H2	119.8	C12A—C13A—C14A	121.4 (7)
C1—C2—H2	119.8	C12A—C13A—H13A	119.3
C2—C3—C4	120.0 (5)	C14A—C13A—H13A	119.3
C2—C3—C8	120.8 (5)	C13A—C14A—C9A	116.7 (6)
C4—C3—C8	119.2 (5)	C13A—C14A—C7A	124.0 (7)
C5—C4—C3	119.5 (5)	C9A—C14A—C7A	119.2 (7)
C5—C4—H4	120.2

Symmetry codes: (i) x+1/2, −y, z+1/2; (ii) −x, −y, −z; (iii) x+1, y, z; (iv) x−1/2, −y, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O4^v	0.82 (11)	2.19 (9)	2.840 (7)	135 (11)
O8—H8B···O7^vi	0.82 (5)	2.26 (11)	2.863 (5)	131 (13)
O9—H9A···O4^vii	0.82 (3)	1.92 (4)	2.734 (6)	172 (7)
O9—H9B···O10	0.82 (5)	1.96 (5)	2.747 (6)	160 (6)
O10—H10A···O3	0.82 (8)	1.95 (8)	2.726 (6)	158 (8)

Symmetry codes: (v) −x+1, −y, −z; (vi) −x+1/2, y, −z+1/2; (vii) −x+1/2, y, −z−1/2.

(II) Poly[[triaqualanthanum(III)-µ-5-sulfonatoisophthalato] monohydrate]

Crystal data

[La(C8H3O7S)(H2O)3]·H2O	F(000) = 880
Mr = 454.14	Dx = 2.317 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2yn	Cell parameters from 5538 reflections
a = 7.9902 (2) Å	θ = 2.3–25.2°
b = 15.4229 (4) Å	µ = 3.50 mm^−1
c = 10.5753 (2) Å	T = 298 K
β = 92.606 (1)°	Prism, colourless
V = 1301.87 (5) Å^3	0.35 × 0.28 × 0.10 mm
Z = 4

Data collection

Bruker APEX CCD area-detector diffractometer	2345 independent reflections
Radiation source: fine-focus sealed tube	2307 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
ϕ and ω scans	θmax = 25.2°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −9→9
Tmin = 0.333, Tmax = 0.713	k = −18→10
6724 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.047	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0252P)^2 + 0.8212P] where P = (Fo^2 + 2Fc^2)/3
2345 reflections	(Δ/σ)max = 0.002
214 parameters	Δρmax = 0.48 e Å^−3
12 restraints	Δρmin = −0.55 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
La1	0.499634 (16)	0.839870 (8)	0.543278 (12)	0.01376 (7)
S1	0.20380 (8)	0.84055 (3)	0.83036 (6)	0.01515 (14)
O1	0.3581 (2)	0.83021 (11)	0.76215 (17)	0.0204 (4)
O2	0.1661 (2)	0.76389 (11)	0.90281 (16)	0.0241 (4)
O3	0.0647 (2)	0.86916 (12)	0.74665 (16)	0.0233 (4)
O4	0.0477 (2)	1.17926 (12)	0.88963 (16)	0.0217 (4)
O5	0.2293 (2)	1.22867 (12)	1.03367 (18)	0.0292 (4)
O6	0.4610 (2)	1.01780 (12)	1.34810 (15)	0.0229 (4)
O7	0.4232 (2)	0.87713 (12)	1.31483 (16)	0.0248 (4)
O8	0.2101 (2)	0.91684 (12)	0.52846 (17)	0.0208 (4)
O9	0.7663 (2)	0.90711 (13)	0.4851 (2)	0.0315 (5)
O10	0.7504 (2)	0.78516 (12)	0.68595 (17)	0.0233 (4)
O11	−0.0152 (3)	1.16204 (12)	0.6450 (2)	0.0295 (5)
C1	0.2272 (3)	1.07620 (16)	0.9956 (2)	0.0175 (5)
C2	0.3096 (3)	1.05780 (16)	1.1107 (2)	0.0185 (5)
H2	0.3373	1.1028	1.1662	0.022*
C3	0.3515 (3)	0.97327 (15)	1.1444 (2)	0.0163 (5)
C4	0.3201 (3)	0.90653 (16)	1.0583 (2)	0.0168 (5)
H4	0.3509	0.8499	1.0786	0.020*
C5	0.2419 (3)	0.92546 (16)	0.9412 (2)	0.0159 (5)
C6	0.1911 (3)	1.00914 (15)	0.9100 (2)	0.0178 (5)
H6	0.1338	1.0203	0.8333	0.021*
C7	0.1668 (3)	1.16634 (15)	0.9702 (2)	0.0179 (5)
C8	0.4194 (3)	0.95473 (15)	1.2780 (2)	0.0162 (5)
H8A	0.156 (3)	0.9052 (18)	0.5920 (16)	0.019*
H8B	0.162 (3)	0.9000 (18)	0.4620 (15)	0.019*
H10A	0.835 (3)	0.8180 (15)	0.687 (2)	0.019*
H10B	0.762 (3)	0.7463 (14)	0.741 (2)	0.019*
H11A	−0.037 (3)	1.2097 (13)	0.616 (2)	0.019*
H11B	−0.001 (4)	1.1613 (15)	0.7244 (16)	0.019*
H9A	0.826 (3)	0.8823 (14)	0.437 (2)	0.019*
H9B	0.772 (3)	0.9600 (10)	0.485 (2)	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
La1	0.01780 (10)	0.01119 (10)	0.01221 (9)	−0.00072 (5)	−0.00025 (6)	−0.00106 (4)
S1	0.0205 (3)	0.0125 (3)	0.0125 (3)	−0.0023 (2)	0.0016 (2)	−0.0012 (2)
O1	0.0248 (9)	0.0201 (9)	0.0167 (9)	−0.0007 (7)	0.0051 (7)	−0.0016 (6)
O2	0.0385 (11)	0.0139 (9)	0.0202 (9)	−0.0065 (8)	0.0065 (8)	−0.0001 (7)
O3	0.0242 (9)	0.0255 (10)	0.0199 (9)	−0.0020 (8)	−0.0031 (7)	−0.0022 (8)
O4	0.0282 (10)	0.0175 (9)	0.0189 (9)	0.0045 (7)	−0.0043 (8)	0.0001 (7)
O5	0.0379 (11)	0.0130 (9)	0.0354 (11)	0.0032 (8)	−0.0132 (9)	−0.0037 (8)
O6	0.0319 (10)	0.0206 (9)	0.0159 (8)	−0.0013 (8)	−0.0024 (7)	−0.0046 (7)
O7	0.0397 (11)	0.0175 (10)	0.0168 (9)	0.0028 (8)	−0.0037 (8)	0.0033 (7)
O8	0.0223 (9)	0.0237 (10)	0.0164 (9)	−0.0014 (7)	0.0004 (7)	0.0007 (8)
O9	0.0320 (11)	0.0156 (10)	0.0483 (13)	0.0000 (8)	0.0183 (9)	−0.0025 (9)
O10	0.0246 (9)	0.0220 (10)	0.0228 (9)	−0.0025 (8)	−0.0041 (7)	0.0028 (7)
O11	0.0338 (12)	0.0302 (12)	0.0241 (11)	0.0013 (8)	−0.0016 (9)	−0.0071 (8)
C1	0.0206 (12)	0.0129 (12)	0.0191 (12)	0.0018 (10)	0.0004 (10)	0.0006 (9)
C2	0.0218 (12)	0.0154 (12)	0.0182 (12)	0.0002 (10)	−0.0004 (10)	−0.0044 (9)
C3	0.0194 (12)	0.0137 (12)	0.0155 (11)	−0.0012 (9)	−0.0007 (9)	−0.0011 (9)
C4	0.0206 (12)	0.0135 (12)	0.0165 (11)	−0.0002 (9)	0.0022 (9)	0.0009 (9)
C5	0.0197 (12)	0.0140 (12)	0.0142 (11)	−0.0015 (9)	0.0031 (9)	−0.0024 (9)
C6	0.0217 (12)	0.0160 (12)	0.0153 (11)	−0.0003 (9)	−0.0014 (9)	0.0017 (10)
C7	0.0229 (13)	0.0128 (13)	0.0181 (13)	0.0004 (9)	0.0009 (11)	0.0004 (9)
C8	0.0183 (11)	0.0167 (13)	0.0137 (11)	0.0008 (9)	0.0006 (9)	−0.0001 (9)

Geometric parameters (Å, º)

La1—O1	2.6260 (17)	O8—H8B	0.829 (16)
La1—O2^i	2.5918 (17)	O9—H9A	0.813 (16)
La1—O4^ii	2.6090 (18)	O9—H9B	0.817 (16)
La1—O5^ii	2.6106 (18)	O10—H10A	0.845 (16)
La1—O6^iii	2.4908 (17)	O10—H10B	0.839 (16)
La1—O7^iv	2.5308 (17)	O11—H11A	0.811 (16)
La1—O8	2.5984 (18)	O11—H11B	0.843 (16)
La1—O9	2.4726 (19)	C1—C2	1.387 (3)
La1—O10	2.5937 (17)	C1—C6	1.395 (3)
S1—O1	1.4654 (19)	C1—C7	1.492 (3)
S1—O2	1.4478 (18)	C2—C3	1.388 (3)
S1—O3	1.4576 (18)	C2—H2	0.93
S1—C5	1.775 (2)	C3—C4	1.390 (3)
O4—C7	1.264 (3)	C3—C8	1.518 (3)
O5—C7	1.263 (3)	C4—C5	1.392 (3)
O6—C8	1.259 (3)	C4—H4	0.93
O7—C8	1.259 (3)	C5—C6	1.388 (3)
O8—H8A	0.835 (16)	C6—H6	0.93
O9—La1—O6^iii	69.69 (6)	O1—S1—C5	106.41 (11)
O9—La1—O7^iv	80.83 (7)	S1—O1—La1	146.45 (11)
O6^iii—La1—O7^iv	105.07 (6)	S1—O2—La1^v	158.74 (12)
O9—La1—O2^i	69.25 (6)	C7—O4—La1^vi	94.62 (14)
O6^iii—La1—O2^i	138.69 (6)	C7—O5—La1^vi	94.57 (15)
O7^iv—La1—O2^i	72.60 (6)	C8—O6—La1^iii	167.74 (16)
O9—La1—O10	68.25 (7)	C8—O7—La1^vii	120.86 (15)
O6^iii—La1—O10	86.59 (6)	La1—O8—H8A	110.2 (19)
O7^iv—La1—O10	140.85 (6)	La1—O8—H8B	106.8 (19)
O2^i—La1—O10	74.31 (6)	H8A—O8—H8B	112 (2)
O9—La1—O8	124.64 (6)	La1—O9—H9A	119.9 (19)
O6^iii—La1—O8	73.65 (6)	La1—O9—H9B	117.7 (18)
O7^iv—La1—O8	70.32 (6)	H9A—O9—H9B	116 (2)
O2^i—La1—O8	136.58 (6)	La1—O10—H10A	114.2 (17)
O10—La1—O8	147.74 (6)	La1—O10—H10B	134.3 (17)
O9—La1—O4^ii	127.10 (6)	H10A—O10—H10B	110.6 (19)
O6^iii—La1—O4^ii	136.73 (5)	H11A—O11—H11B	114 (2)
O7^iv—La1—O4^ii	116.33 (6)	C2—C1—C6	119.6 (2)
O2^i—La1—O4^ii	69.77 (6)	C2—C1—C7	119.0 (2)
O10—La1—O4^ii	69.56 (6)	C6—C1—C7	121.2 (2)
O8—La1—O4^ii	108.08 (6)	C1—C2—C3	121.1 (2)
O9—La1—O5^ii	142.91 (7)	C1—C2—H2	119.4
O6^iii—La1—O5^ii	142.63 (6)	C3—C2—H2	119.4
O7^iv—La1—O5^ii	73.53 (6)	C2—C3—C4	119.5 (2)
O2^i—La1—O5^ii	77.67 (6)	C2—C3—C8	119.2 (2)
O10—La1—O5^ii	118.65 (6)	C4—C3—C8	121.1 (2)
O8—La1—O5^ii	70.85 (6)	C3—C4—C5	119.2 (2)
O4^ii—La1—O5^ii	49.67 (6)	C3—C4—H4	120.4
O9—La1—O1	130.80 (7)	C5—C4—H4	120.4
O6^iii—La1—O1	72.17 (6)	C6—C5—C4	121.4 (2)
O7^iv—La1—O1	139.42 (6)	C6—C5—S1	119.30 (18)
O2^i—La1—O1	136.30 (5)	C4—C5—S1	119.29 (19)
O10—La1—O1	79.68 (6)	C5—C6—C1	119.0 (2)
O8—La1—O1	70.20 (6)	C5—C6—H6	120.5
O4^ii—La1—O1	68.46 (5)	C1—C6—H6	120.5
O5^ii—La1—O1	85.05 (6)	O5—C7—O4	120.4 (2)
O2—S1—O3	113.42 (11)	O5—C7—C1	119.8 (2)
O2—S1—O1	111.81 (11)	O4—C7—C1	119.7 (2)
O3—S1—O1	111.69 (11)	O7—C8—O6	123.4 (2)
O2—S1—C5	106.65 (11)	O7—C8—C3	118.0 (2)
O3—S1—C5	106.32 (11)	O6—C8—C3	118.5 (2)

Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (ii) −x+1/2, y−1/2, −z+3/2; (iii) −x+1, −y+2, −z+2; (iv) x, y, z−1; (v) x−1/2, −y+3/2, z+1/2; (vi) −x+1/2, y+1/2, −z+3/2; (vii) x, y, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O3	0.84 (2)	1.90 (2)	2.731 (2)	171 (3)
O8—H8B···O11^viii	0.83 (2)	1.86 (2)	2.648 (3)	159 (2)
O9—H9A···O11^ix	0.81 (2)	1.90 (2)	2.690 (3)	164 (2)
O9—H9B···O8^ix	0.82 (2)	1.91 (2)	2.726 (3)	176 (2)
O10—H10A···O3^x	0.84 (2)	2.07 (2)	2.872 (3)	159 (2)
O10—H10B···O5^iii	0.84 (2)	2.41 (3)	2.970 (3)	125 (2)
O10—H10B···O7^i	0.84 (2)	2.41 (2)	3.140 (3)	146 (2)
O11—H11A···O5^xi	0.81 (2)	2.23 (2)	2.859 (3)	134 (2)
O11—H11B···O4	0.84 (2)	1.79 (2)	2.626 (3)	169 (2)

Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (iii) −x+1, −y+2, −z+2; (viii) −x, −y+2, −z+1; (ix) −x+1, −y+2, −z+1; (x) x+1, y, z; (xi) x−1/2, −y+5/2, z−1/2.